Metal treatment



United States Patent 2,935,432 METALTREATMENT Ludwig K. Schuster, Philadelphia, Harvey A. Whitenight, Norristown, and William A. Jung, Jr., Philadelphia, Pa., assignors, by direct and mesne assignments, of

j one-half to Reilly-Whitem-an-Walton Company; Whitemarsh Township, Montgomery County, Pa., a corporation of Pennsylvania, and one-half -to Kelsey-Hayes Company, Detroit, Mich., a corporation of Delaware No Drawing. ApplicationApril 2, 1957 Serial No. 650,072

18 Claims. (Cl. 148-615) I p The present invention relates to the treatment of metal surfaces, particularly for improving the characteristics for organic compound having from 12 to 30carbon atoms in a connected group, about 0 to 90% by weight of a substantially non-volatile organic metal lubricant, about 1% to 15% water by weight and 2.5 to by weight of an acid selected from. the class consisting of p hosphoric and phosphorous acids, said water and said acid being dissolved in the organic material, and the preparation being a stable single phase liquid at a temperature at least as low as 80 C.

The hydrophilic material can be an amide of jfatty acids and/or resin acids, the amide being substituted either on the amine group or elsewhere withhydrophilic radicals of the class consisting of hydroxy, methoxy, ethoxyfamine and imine radicals, and there'being a total of at least three of said hydrophilic radicals per 12 to carbon group. Amines of compounds having the above carbon chains are also suitable. Where the hydrophilic radicals are amines or imines, best results are "obtained if they are unsubstituted or if substituted, at least one of the substitnents has a carbon chain no more than four carbons in length. Preferred amides are those formed by condensing in s'ubstantially equimolar proportions fatty acids having twelve to twenty-two carbon atomsiper molecule, and polyalkylene polyamines of alkyl groups having no more than four carbon atoms per group. .Such amides can also be made by reacting the above polyalkylene polyamines with esters of the'abo've' acids. Glycerine tri-fatty acid esters, represented by the natural fats and oils, readily react by heating a mixture of the reactants at 210,to 220 F., to form the amides .and

. glycerine. If the quantity of: amine used is less" than 7 A feature of the present invention is that the above.

preparations are quite stable. They can for example ice be kept at temperatures as high as 200. "F. without appreciable loss by .volatilization or chemical change. When the preparation is applied to the surface of reactive metal, such as iron, it will react with the. surface of the metal to form an adherent layer of-a metal phosphate complex which in combination with the balance of the applied mixture, makes an exceedingly'effective and tightly bonded lubricant coating. 1 Both the water and the phosphoric acid are dissolved in theremai'ning material of the mixture and there is accordingly no tendency for an aqueous component to settle out on stand; ing. Furthermore, because of its dissolved condition, the water does not evaporate very readily from the mixture.

Similar mixtures in which water is present as a separate phase or as a continuous phase, show much higher water vapor pressures and undergo rapid water loss, particularly at elevated temperatures. In addition, contact of the metal-with a two-phase system causes the phosphate formation to take place in a spotty manner, whereas" a single-phase system provides uniform distribution of the reactive ingredients over the entire surface being treated, thus resulting in a uniform deposition of the metal phosphate complex. i Y

I A minimum of 1% water should be used as pointed out above, since without this water the phosphoric acid in the formulation does not attack the metal. At least about 5% phosphoric acid is preferably present when only 1% of water is used, since the phosphating of the metal is a little slow otherwise. At about 4% or more water content the metal attack is quite rapid over the entire range of said concentrations. A 4% or larger water content is more readily obtainedif *the coating preparation includes such coupling agents asan alkylene glycol, an alkylene glycol ether and/or a fatty acid. From 2 to 15% of an alkylene glycol or alkylene glycol ether having a chain of from 3 to 8 carbon atoms per molecule is quite effective, as is from 2 to 15% fatty acid. Some of these alkylene glycol ethers are quite volatile and are accordingly not preferred in high temshould be noted that the amides describedyabove are in,

themselves very good metal lubricants.

The coating preparation of the present vention can accordingly be very effectively used as a bath in which metal articles are immersed, removed and then subjected The bath will.

to the desired cold working operations. remain substantially uniform in composition and effectiveness, even though it is kept at a temperature as high as 200 F. for periods of a day or more. The reaction of the metal with the phosphoric acid is generally sufficiently complete in about one or two'minutes, but the dwell of metal in the bath can be made short enough so that the principal result is to cause the coating preparation to coat the immersed surface. After the immersed articles are removed, the desired coating is obtained upon standing a minute orso to permit the" phosphoric acid to develop the desired amount of metal 'phosphate coiriplex. The period of immersion in the bath, or the contact time with application rolls, brush, spray, etc., need not be more than a few secondsfor less, since the applied film carries the reactive ingredients whichform I the metal phosphate complex coating. If, however, an extremely difficult operation is to be performed, a longer period in the treating bath will result in the formation:

Example I 49.6% partial fatty amide formed by heating 152 parts of tallow (free fatty acid, 3% maximum) together with 13 parts of diethylene triamine at 210 F.220 F. for three hours.

3.3% oleic acid.

7.4% water.

10.1% orthophosphoric acid, 75% commercial grade.

3.3% parafiin wax, melting point 124-126 F.

4.0% hexylene glycol.

9.3% methyl ester of pigskin oil fatty acids.

13.0% mineral oil, 100 Saybolt Universal seconds at The above ingredients are very readily blended in the liquid state to form a single phase liquid of fairly low viscosity.

Other examples of composition of the present invention are as follows (all proportions are by weight):

Example II 30.0% lard oil.

25.0% fatty amide prepared by heating one mole of oleic acid (282 parts) together with one mole of diethanolamine (105 parts) until the acidity (as oleic acid) is less than 5%.

7.0% orthophosphoric acid, 85% commercial grade. 1.0% water.

6.0% oleic acid.

6.0% hexylene glycol.

25.0% parafiinic mineral oil, 225 Saybolt Universal seconds at 210 F.

Example III 20.0% fatty amide prepared by reacting 284 parts of stearic acid with 105 parts diethanolamine at 300 F. until the acidity (as stearic acid) is less than 5 50.0% parafiinic mineral oil (100 Saybolt Universal seconds at 100 R).

10.0% oleic acid.

10.0% hexylene glycol.

8.0% orthophosphoric acid, 75%. 2.0% water.

This composition is a clear liquid above about 100 F., and a pasty solid at room temperature (70 80 F.). As much as 6 additional parts of water can be added to accelerate coating formation and still maintain the single phase composition.

Example IV 19.4% fatty amide (as in Example III).

29.1% No. 1 lard oil.

24.3% paraffinic mineral oil (100 Saybolt Universal seconds at 100 F.).

9.7% oleic acid.

9.7% hexylene glycol.

6.8% orthophosphoric acid, 85

1.0% water.

This composition is a clear liquid above about 115 F., and a pasty solid at room temperature (70 F.80. F.).

4 Example V 48.1% fatty amide prepared by reacting 282 parts of oleic acid with 105 parts of diethanolamine at 5 300 F. to 310 F. until the acidity (as oleic acid) is less than 5%. 38.5% No. 1 lard oil.

9.6% orthophosphoric acid, 75 3.8% water.

This composition is a clear viscous liquid at room temperature (70 F.80 F.), becoming more fluid with increasing temperature.

Example VI This composition is a clear liquid at a temperature above about 95 F. and a pasty solid at room temperature (70 F.80 F.).

Example VII 30.0% raw linseed oil partial amide prepared by heating 100 parts of raw linseed oil with 8.4 parts of diethylene triamine at 200 F. for 3 hours.

40.0% raw linseed oil.

10.0% oleic acid.

10.0% hexylene glycol.

7.1% orthcphosphoric acid, 85%.

2.9% Water.

This composition is a clear liquid. Addition of small quantities (0.1% to 0.5%) of dryer (such as cobalt linoleate) will accelerate the hardening of the deposited film.

Example VIII 72.7% fatty amide prepared by reacting 282 parts of oleic acid with 105 parts of diethanolamine at 300 F. to 310 F. until the acidity (as oleic acid) is less than 5%. 17.7% orthophosphoric acid, 85%.

7.3% hexylene glycol.

2.3% water.

This composition is a clear liquid at room temperature.

Example IX 33.9% fatty amide prepared by reacting 284 parts of stearic acid with 105 parts diethanolamine at 300 F. until the acidity (as stearic acid) is less than 5 30.3% No. 1 lard oil.

8.1% oleic acid. 8.4% phosphorous acid, 70%.

11.2% water.

I orthophosphoric acid 35 14.3 hexylene glycol. 1.7% .water.

[This composition is a clear liquid at room temperature.

Theimportant ingredients of the above compositions ofExamplesl to XI are'thefatty amide or amine, either of fwhich m'akes a good lubricant carrier, a good lubricaiitbyitselffis'miscible withthe other lubricants, and makes possible the solution of. water and phosphoric acidinthe, mixture without separation. Any oil such as mineral 'oil, or -fatty oils such: astallow, lard oil, palm.

oil, palm kernel oil, mustardfseed oil andpeanu't oil can be used as a supplemental lubricant, and sharply reduce the, frictional resistance 7 to surface forming operations.

Drying or. semi-drying oils 'such'as linseed oil, tung oil and soyabean oil may'be used in'the lubricant portion to obtain relatively hard,jdry, tenacious films such as may 'bedesired for extremely severe cold working operations. -Rosin amine such as that prepared by hydrogenating the nitrile of rosin (abietic acid) is also a good supplemental'lubricant.

-The hydrophilic amide can be formed of any fatty acid and/or resinacid; .The group of 12 to 30 carbon atoms canibe-iii, one unbranched chain, as-in the fatty acids, oripfusedrings, asin a resin acid such as abietic acid. They can -also be in brafiched chains as in, betaethyl decano ic acid, ;or in f combinations of chains I and rings as in alphanaphthyl acetic acid. It appears that the acid should have-a, strongly lyophilic character which it does notfde'velop'unlessthe appropriateinumber of carbon atoms 'arelinkd directly to each other as a group. Linkages byw'ay 'or oxygen, sulfur, nitrogeriror the like are not effective for this purpose. These acids can be satu rated or unsaturated, as roriesampie stearic acid, oleic acid; palmitic a'cid, linoleic aci h fully hydrogenated. pirnaric acid and even omegacarboxy stearic acidr lhe most. desirable commercial acids are those containing 16. or 1 8;carbon atoms. The preferred compositions have 10,;to 40% ofthepolyalkylene polyamine reaction productsof; these acidswith 30 to 80% of an organic 'oily lubricant,3 4to 15% water and 5 to 20% phosphoric acid, all percentages being by weight.

The acids are condensed with amines as pointed out above, and the condensationjis carried out so that the product contains at least 3 hydrophilic radicals per moleculje i This appears to be essential in order to have the desiredamo'unt ofwater dissolved in the coating prepara tibtli Antinesisuitable'for condensation in accordance ylenetriamine; N,N,N'-trihydroxyethyl ethylenediamine;

dibutanolamine; diisopropanolamine; tetraethylene pent amine; phenyl diethanolamine; N-(2-hydroXyPr0pyl) e'th ylenediamine; and triglycolamine The Ethomeen of Example XI is not a effectivela water carrier as the amides. Relatively large proportions of fatty acid and glycol or glycol ether are needed' formulations relying on such a carrier. 3 1 I 5 Similar materials such as polyethoxylated fattyalcohols; (alcohols prepared by reducing esters ofv C acids with sodium and'rnethyl isobutyl carbinol), as forexample that formed b'y condensing onemole' ofialcohols cor'r'e; sponding to tallow fatty acids, with 6 moles of ethylene oxide, will also provide mixtures that dissolvethe appro priate amount of water but such mixture'swillnot be as; stable asthefatty acid amides and undergodeterioration' at temperatures of 60 C. or higher. In general, a' chain of alkoxy groups is equivalent to half as many'separate alkoxy groups in providing hydrophilic qualities; I

As in Example I,.the coating preparations of the present invention can contain an' appreciable amount, up to-20% of paraflin or fat that is solid at 80. F. Hydrogenated fat or oil, or petroleum, natural or syntheticwaxes can, be so used. In addition, low viscosityadditives, such as the methyl ester of Example I, help to lower the viscosity, and to thereby facilitate the application of the coating. Relatively low viscosity mineral oil can .be usedfor the same reason. 'It is also preferred that abouthalf the lubricant be 'fatty material as against hydrocarbon lubricant. 3

The amount of phosphoric acid as specifiedabove, re fers to thetotal phosphoric acid. Where thepreparation includes basic groups such as amine andarn'ide radicals in the fatty amine or amide, some of the phosphoricacid' will be bound up by salt formation. The bound-upportion does not contribute any amount of free phosphoric acid and will in general not cause any significant phose' phate-forming reaction with the metal if the wat'er content is less than about 4%. Howeverg the, amine phosphate generally undergoes some hydrolysis, particu,- larly where the coating mixture has a water content-in" the high end of the range. The phosphoric acid so re-.,,- leased by this hydrolysis will not produce coatings of"- sufilcient magnitude to'be ofpractical importance, and can accordingly be neglected. Metaphosphoric acid and pyrpphosphoric acid can be used insteadrpf orthophos phoric acid, butthey gradually combine withsorn'e of] the water in the bath during this conversion; This bound-:1 up water is not efiective in contributing any of the desired final water content. However, most commercial grades f of phosphoric-"acid contain some water. which should: be 7 a taken into account in the formulation. Phosphorous acid can be substituted 'for part or all of the phosphoric acid, a

condensing trichlorethylene, most, but. not all of the organic coating is removed, the remainder bein'gthesol vent insoluble metal phosphate. complexwhich contains,

some of the organic material. This bound-upffresidual 3 organicmaterial canuot be entirely removed by;

2-propyl-2-amino l,3-propandiol;,

degreasing; the complex phosphate must first be decomposed. chemically to release the organic material. Degreased coatings of 40 to as much as 2500 milligrams per square foot are highly effective for even severe cold working and also give good corrosion resistance. Furthermore, the degreased surface, before or after working, can be directly painted without removal of any of the coating. In fact, the residual coating causes paint to adhere better and gives the metal more corrosion resistance.

It is a further feature of the present invention that the metal treated with the above preparation can have a surface that is prepared in any way. For example, ferrous surfaces can be either sand blasted, shot blasted, pickled or either hot or cold rolled, and in addition can have light surface films of oil and/or rust. Sand blasted surfaces seem to be the most active and form the desired metal phosphate layer most rapidly. Shot blasted surfaces are somewhat slower to react. Pickled surfaces and ordinary cold-rolled surfaces may take longer than blasted surfaces. The presence of thin films of oil such as palm oil or mineral oil, ordinarily applied to bare metal in order to prevent prompt corrosion, does not significantly interfere with the practice of the present invention. The coating preparation appears to dissolve in or through an oil layer quite rapidly and the development of the phosphate coating is not appreciably prolonged.

In addition to the above, the coating preparation will also work very effectively with a metal surface that is covered with some oxide or even scale. Heavy scale or thick oxide film is only partially converted to phosphate, but the partially converted material is suitable for working operations. A cold rolled steel or even a pickled steel need not be completely free of rust for the purpose of the present invention, and will be suitable for direct application of the coating preparation without any preliminary treatment.

The coating preparation can be applied by dipping, flooding, brushing, rolling or even spraying. After the application the coated metal can be permitted to stand as long as desired. One convenient way of practicing the invention is to roller coat metal sheets with the coat ing preparation and then to stack them on top of each other. Suflicient coating preparation will remain between the individual sheets in the stack to give the desired lubrication after the phosphate layer has developed.

Detailed specific examples of the use of the coating preparation of the invention are as follows:

Example XII Tube drawing.-SAE 1015 steel tubing with an outside diameter of 0.875" and a wall thickness of 0.058" was pickled in 20% sulphuric acid by weight for approximately minutes. It was rinsed to remove the residual pickle acid and air-dried.

The tubing was then submerged in the coating preparation of Example 11 and maintained at a temperature of 135 F. for 5 minutes. The tubes were removed from the coating bath, allowed to drain, and then drawn to an outside diameter of 0.705" and a wall thickness of 0.040". This represents a reduction of 44.2% and is the maximum usually attempted on this type steel.

There was no difliculty in drawing and no scratches on the tubes or dies resulted. The finish was excellent. The prior art treatment usually used for such drawing is the separate application of a phosphate coating after pickling, followed by rinsing, and then dipping into a super-fatted soap type lubricant.

Example XIII developed a slight rust coat'prior to the application of the coating preparation, but this rust did not interfere with the drawing operations which were conducted. The coating preparation of Example I was heated to F. and brushed on the bars. After about l hour interval, these bars were given a reduction of inch diameter which is considered aheavy reduction in bar drawing.

The drawing was conducted without any difliculty and there was a noticeable improvement in finish over that produced by the prior art treatment which is to apply to heavy lime coating after pickling, and then lubricate with an oil circulated at the draw bench.

Following the procedure of Example IV, bars of SAE 4340 steel 2% inches in diameter and hexagonal bars of SAE 1144 steel were drawn without any difliculty using the standard reductions employed with the conventional lime coating and oil application. In all cases, there was a decided improvement in finish with the treatment of the present invention.

Example XIV Forming-Coils of low carbon steel (SAE 1010) approximately 20 inches wide and 0.071 inch thick were shot blasted in order to remove mill scale which was present as a heavy surface layer. The coating preparation of Example I was applied to the shot blasted surface by roller coating at the rate of 2.8 pounds per ton of steel or approximately 1 pound for 580 square feet of steel surface. After application of the coating preparation, the steel was formed into conduit boxes of various sizes and shapes. Forming of the boxes was accomplished without any difliculty whatsoever with extremely low breakage and with a punch life of over 400,000 pieces per punch. The punch life with prior art lubricants on the same steel surface had averaged less than 100,000 pieces per punch.

After forming, the residual film from the coating preparation was removed by alkali cleaning and the boxes were then galvanized without any ditficulty.

Example XV Forming-The coating preparation of Example I was heated to 140 F. and applied, using transfer roller coating, to both surfaces of hot rolled and freshly pickled SAE 1010 steel 28 inches wide and 0.075 inch thick. The metal was coiled immediately after coating. The metal temperature was F. at the point of application and cooled to room temperature after a period of 10 hours.

These coils of metal were rolled on a S-stand tandem mill, as normally employed in the cold rolling of tin plate, and the rolling was carried out the day following the application of the coating preparation. The average mill loads obtained with the coating preparation on the metal are given below as compared to prior art practice:

The Coating Synthetic Roll Stand Preparation Palm Oil of Example I (Prior Art) Am a. Am a. #1 p 110 p #2 1,190 1, 980 #3 2, 030 2, 200 #4 1, 900 1, 070 #5 2,060 2,160

It will be noticed that a definite reduction in load was v P e were then degreasedforpm 1101 in, trichlor ethylene vapors.

" These panels were then-spray'painted using a urieai and melamine modified alkyd baking enamel (Pratt and Lambert #0358), thickness 0.7 to 1.0 mil, baked for 10 minutes at 350 F. After drying'they were subjected to a 15 day salt spray test u sing-a saltsolution of 20% the conventional type phosphate coating in all cases.

Example XVII Deep drawing.The blanks used were of deep drawing quality low carbon steel (SAE 1020), octagon shape, 32%" x 30" x 0.062". The blanks had a film of rust preventive palm oil on the surface, which was not removed. The coating preparation of Example I was applied with cloth rolls, at room temperature.

Within two minutes of application, the blanks were drawn in a 400 ton press into a gasoline pump dome measuring about 103 deep, 21" long, 13%" wide, with an average wall thickness of 0.049". The dome had rounded corners and an oval shaped bottom.

Several hundred domes were drawn with the coating and the lubricant removed by alkali cleaning. No difficulties were encountered and the operation was entirely satisfactory. In order to obtain equally satisfactory drawing, the prior art practice is to clean the slushing oil from the steel, rinse, apply zinc phosphate coating, rinse, apply soap-borax type dry film lubricant, and dry carefully in order to remove all of the moisture from the soap borax film. In this case the single application of the coating preparation of the present invention replaces a six-step process.

The coating preparation of the present invention can be used with any metal that reacts with phosphoric acid. Low alloy steels, that is steels containing less than of other alloying metals, are suitable, including low carbon steels, such as SAE 1010, SAE X1040; high carbon steels, such as SAE 1095; molybdenum steels, such as SAE 4150; chromium steels, such as SAE 5140; chromium vanadium steels, such as SAE 6145; nickel-chromium steels, including SAE 3220; tungsten steels, such as SAE 7260; and silicon-manganese steels, such as SAE 9255. Coatings can also be formed on aluminum and other non-ferrous metals which react with phosphoric acid. Metals which do not react with phosphoric acid, such as stainless steels, can also be lubricated since the coating preparation will function in the same manner as normal boundary lubricants in these cases.

Because of'the absence of significant amounts of volatile ingredients, there is very little fire hazard involved in the use of the above formulations even at high temperatures. The use of supplemental thinners or solvents is not desirable for this reason and also because these dilute the lubricating effectiveness. The dilution of the formulations of Example X with an equal weight of kerosene will for example give significantly reduced lubricity, although 4 hour standing of iron coated with this preparation will raise the lubricity back to a value approaching that of the undiluted preparation.

Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

What is claimed: 1. A metal coating preparation consisting essentially of a hydrophilic organic compound having from 12 to 30 carbon atoms in a connected group, up to 90% by weight of substantially, non-volatile organic metal lu- 75 bricant, about 1% to15.% water byweight, and 2.5 to.

temperature at least as lowas C.

'2. The combination of claim 1 in which the" hydrophilic compound is selected from the class consistingof amines and amides that are substituted with hydrophilic radicals of the class consisting of hydroxy, methoxy, ethoxy, amine and imine radicals, and there being a total of at least three hydrophilic radicals per 12 to 30 carbon group.

3. The combination of claim 1 in which the hydrophilic compound is the amide formed by condensing, in substantially equimolar proportions fatty acids and polyalkylene polyamines of alkyl groups having no more than four carbon atoms per group.

4. The combination of claim 3 in which thepreparation also contains from 2 to 15% fatty acid and from 2 to 15% of a member of the group consisting of alkylene glycols and ethers of alkylene glycols, said member having a chain of from three to eight carbon atoms per molecule. Y i

5. The combination of claim 1 in which the preparation also contains from 2 to 20% paraflin wax.

6. A metal coating preparation consisting essentially of 10 to 40% by weight of the equimolar reaction product of a fatty acid having 14 to 20 carbon atoms per molecule with a polyethylene polyamine 30 to 80% by weight of an organic lubricant oil having a chain of at least 12 connected carbon atoms 4 to 15% Water by weight, and

5 to 20% phosphoric acid by weight,

the water and acid being dissolved in the remaining ingredients.

7. The composition of claim 6 in which about half the lubricant oil is a fatty oil.

8. A metal having its surface covered with a layer of the composition of claim 1, said layer weighing at least 400 milligrams per square foot of surface that it covers.

9. A ferrous metal having its surface covered with v 11. The method of claim 10 in which the contacted metal surface is a sand blasted ferrous surface.

12. The method of claim 10 in which the contacted i V 7 metal surface is shot blasted ferrous surface.

13. The method of claim 10 in which the contacted metal surface is a pickled ferrous surface.

14. The method of claim 10 in which the contacted metal surface is rolled ferrous surface.

15. The method of claim 14 in which the contacted metal surface is a cold worked one.

16. The method of claim 14 in which the contacted Q metal surface is a hot worked one.

17. The method of preparing cold worked metal objects, said method being characterized by the steps of providing the metal precursor, coating it with the composition of claim 1 to form on its surface a lubricant coating suitable for cold working, degreasing the coated metal, and cold working the degreased material.

18. The method of claim 17 in which the cgated sur 11 7 face i a ferrdus surface and aftr cold working is di- 2,739,915 rectly painted over. the degreased coating. 2,767,111 2,857,298

References Cited in the file of this patent UNITED STATES PATENTS 5 1,936,534 Albrecht Nov. 21, 1933 6 5, 7 2,712,511 Orozco July 5, 1955 1,075,839

, v 12. Schuster et a1. Mar. 27, 1956 Otto et' a1. Oct. 16, 1956 Smith Oct. 21, 1958 FOREIGN PATENTS Great Britain June 24, 1949 France Apr. 14, 1954 

1. A METAL COATING PREPARATION CONSISTING ESSENTIALLY OF A HYDROPHILIC ORGANIC COMPOUND HAVING FROM 12 TO 30 CARBON ATOMS IN A CONNECTED GROUP, UP TO 90% BY WEIGHT OF SUBSTANIALLY MON-VOLATILE ORAGNIC METAL LUBRICANT, ABOUT 1% TO 15% WATER BY WEIGHT, AND 2.5 TO 25% BY WEIGHT OF AN ACID SELECTED FORM THE CLASS CONSISTING OF PHOSPHORIC AND PHOSPHOROUS ACIDS, SAID WATER AND SAID ACID BEING DISSOLVED IN THE ORGANIC MATERIAL, AND THE PREPARATION BEING A STABLE SINGLE PHASE LIQUID AT A TEMPERATURE AT LEAST AS LOW AS 80*C. 